Acid wool dyestuff of the anthraquinone series and process of making same



July 31, 1934 AGED W001. DYESTUFF OF THE ANTHRA- QWNONE SERIES ANDPROCESS OF MAK- KNG SAME Berthold Stein, Mannheim-on-the-Rhine, and

Ernst IEonold, Frankfort-on-the-Main-Fechenheirn, Germany, assignors toGeneral Aniline Works, Inc, lflew York, N. Y., a corporation of DelawareNo Drawing. Application April 11, 1932, Serial No. 604,652. GermanyApril 15, 1931 3 Claims.

This invention relates to acid Wool dyestufls of the anthraquinoneseries and to a process of making same.

The process of the invention comprises replacing either halogen atom oflA-diamino-Zfi-dihalogen-anthraquinone by a mercapto and the latter by asulfonic acid group, and replacing the second halogen atom by an'aryloxy group and advantageously sulfonatingthe latter.

The following scheme of formulae illustrates the said reactionsz- Theintroduction of the aryloxy group (steps b and e) is effected bytreating the halogen com: pound (I or IV) with an aromatic hydroxy-com--pound in the presence of an acid bindin agent, advantageously at thetemperature of the boiling water-bath.

The introduction of the mercapto group (steps a, and d) is carried outby acting on the halogen compound (I or III) with an alkali metalsulfide.

The transformation of the mercapt-o group or also the correspondingdisulfide group into the sulfonic acid group (steps 0 and f) which isthe most surprising step of this process, is effected by treating themercapto compound (II or V) in an alkaline or acid medium with anoxidizing agent of the group consisting of peroxides and per-salts, suchas, for example, with hydrogenor an alkalimetal-peroxide, perborate orpersulfate. ln'this reaction the amino groups which are known to be 1easily attacked by oxidizing agents remain intact.

The sulfonic acids thus obtained are valuable dyestuffs for Wool andacetate silk. They exhibit good fastness and levelling power. The 1.4"diamino-3-halogen-anthraquinone-2-sulfonic acids 1 (IV of the aboveformulae) yield blue, the L l-diamino-3-aryloxy-anthraquinone-sulfonicacids (VI of the above formula) yield violetish blue shades. Some of thelatter sulfonic acids (VI) are described in the copen'ding U. 5..application Serial No. 557,943, filed August 18, 1931.

By aftertreating (step 9) the latter compound (VI) with sulfonatingagents a further sulfonic acid group enters into the aryl residuewhereby dyestuffs (VII) of an especially good solubility may beobtained.

In order to further illustrate our invention the following examples aregiven the parts being by weight and all temperatures in centigradedegrees; but it is, however, to be understood, that our invention is notlimited to the particular products or reacting conditions mentionedthere Example 1 To a solution of 23 parts of the sodium salt of l.4diamino-3chloro-anthraquino11e-2-mercaptan in 1000 parts of water, l0parts of hydrogen peroxide of 30% are added at room temperature whilestirring. After a short time the shade of the solution turns from bluishviolet to blue. The mass is further stirred for some hours and then theformed sulfonic acid is isolated in the form of its sodium salt by theaddition of common salt. I

The sodium salt of the 1.4-diamino-3-chloroanthraqninone-Z-su1fonic acidthus obtained corresponds probably to the formula:

The new product is easily soluble in Water with a blue color and yieldsa colorless solution in concentrated sulfuric acid, which becomes blueupon the addition of parafornialdehyde.

The oxidation may be carried out with the same success in the presenceof free alkali.

' Example 2 30 parts of 1. i-diamino-3-chloro-anthraquinone-Z-mercaptainare disolved in 581) parts of con centrated sulfuric acid and oxidizedat LEO-30 C. by slowly adding parts of potassium-persulfate. Afterhavingstirred for several hours the formed sulfonic acid is isolated in theform of the difficultly soluble sulfate by means of ice-water.

Then the mass is dissolved in hot water with the addition of sodiumcarbonate and common salt is added to the solution. The compound thusobtained is identical with that described in Example 1.

The reaction runs in the same manner, when instead of 1.l-diamino-3chloro-anthraquinone- Z-mercaptan a heavy metal salt (e. g.zinc-mercaptide) or the disulfide is used.

By starting from IA-diamino-ZB-bromo-anthraqifinone-Z-rnercaptan aproduct of quite similar properties is obtained.

Example 3 A solution of 35 parts of the sodium salt of 1.4-diamino--3-chloro-anthraquinone-2-sulfonic acid (see Examples 1 and 2),10 parts of sodium carbonate and 20 parts of phenol in 1500 parts ofwater is boiled for some hours under a reflux condenser, advantageouslywhile stirring. The remaining excess of phenol is dissolved by theaddition of caustic alkali lye and the formed 1.4ldiainino- 3-phenoxyanthraoi; .one- 2 -sulfonic acid is separated in the form 0. assodium salt by the addition of sodium chloride. The dyestuii thusobtained is identical with that described in U.S. application Serial No.557,943, filed August 18, 1931, Example 1.

Example 4 In the same manner as described in Example 3 by using p-cresola new dyestuff is obtained which yields a colorless solution inconcentrated sulfuric acid; after the addition of paraiormaldehyde thissolution becomes blue. The dyestuii dyes wool from an acid bath fastequal navy blue shades and corresponds probably to the followingformula:

Example 5 By effecting the condensation according to Example 3, insteadof with phenol, with the same quantity of resoroinol, a dyestuff isobtained dyeing wool bluish violet shades; it corresponds probably tothe formula:

1? Osoma O II I o N112 on Dyesuffs dyeing similar shades are obtained,for example, by using guaiacol, m-hydroxy-benzoic acid, xylenols, etc.All these dyestuffs possess good levelling capacity.

Example 6 A solution of 1D parts of the sodium salt of 1.4-diamino-3-chloro-anthraquinone-2-sulionic acid (described in Examples 1and 2) in about 300 parts of water "s condensed in the presence of 15parts of caustic soda lye (specific gravity 1.3) with 20 parts ofc-naphthol at the temperature of the boiling water-bath. Thecondensation product, which is separated from the solution by theaddition of sodium chloride, dyes wool from an acid bath navy blueshades. The dyestuii corresponds probably to the following formula:

tained by condensation with u-naphthol.

Example 7 To a solution of 38 parts of the sodium salt of1.4-diamino-B-phenoxy-anthraquinone-Z-mercaptan in 1000 parts of water,40 parts of hydrogen peroxide (30%) are added at room temperature Whilestirring. After some hours stirring the formed 1.l-diaminQ-S-phenoxy-anthraquinone-2-sulfonic acid is separated from thebluish q violet solution, which is filtered if necessary, in IMO theform of its sodium salt by the addition of sodium chloride. The dyestuffthus obtained is identical with that of Example 3.

With the same result the oxidation may be carried out with similaroxidation agents, such as perborates or alkali-peroxides.

The sodium salt of the 1.4-diamino-3-phenoxyanthraquinone-2oneroaptanused as starting material may be obtained in the usual manner bytreating 1. dia1nino-3phenoxy-2-halogen-an- 1m thraquinone (see U. S.Patent No. 1,038,589) in an alcoholic solution with an excess of sodiumdisulfide.

Example 8 4-3 parts of the sodium salt of L l-diaminO-3-5-naphthoxy-anthraquinone-2-rnercaptan (obtainable in an analogous mannerto the phenoxyderivative) are oxidized according to Example 1. Thedyestuff thus formed is identical with that of Example 6.

We claim:-

1. A process which comprises treating L l-diamino-Z-niercapto 3 halogenoanthraquinone with an oxidizing agent of the group consisting ofperoxides and per-salts and treating the 1.4-

diamino-3-halogeno-anthraquinone 2 sulfonic acid thus formed with acompound of the group consisting of phenols and napht-hols in thepresence of an acid-binding agent.

2. A process which comprises treating1.4-diamino-2-mercapto-3-chloro-anthraquinone with an oxidizing agent ofthe group consisting of peroxides and per-salts and treating the1.4-diamino 3 chloro-anthraquinone-z-sulfonic acid 135 thus formed withresorcinol in the presence of an acid-binding agent.

3. The acid wool dyestuff of the anthraquinone series corresponding tothe formula lyre SO3H 0 NH: OH

which compound dyes wool from an acid bath bluish violet shades.

BERTHOLD STEIN. ERNST I-IONOLD.

